JPH1025422A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. possessing excellent flame retardancy, heat resistance, and impact resistance by mixing a thermoplastic resin, a polycarbodiimide, an arom. compd. contg. a functional group and/or an arom. oligomer together in a predetermined mixing ratio. SOLUTION: A thermoplastic resin (A) (e.g. a rubber-reinforced styrene resin), a polycarbodiimide (B), and an arom. compd. contg. a functional group (C) and/or an arom. oligomer are mixed together in such a mixing ratio that the content of the component (C) is 0.1 to 50 pts.wt. based on 100 pts.wt. in total of the components (A) and (B), thereby obtaining a resin compsn. If necessary, 1 to 50 pts.wt. flame retardant (e.g. brominated polystyrene) may be further incorporated. Specific examples of preferred arom. compds. contg. a functional group as the component (C) include p-hydroxybenzoic acid, terephthalic acid, and 2-carboxybenzamide. Specific examples of preferred aromatic oligomers as the component (C) include aromatic polyamide oligomers and polycarbonate oligomers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to flame retardancy, heat resistance,
The present invention relates to a resin composition having excellent impact resistance.

2. Description of the Related Art Thermoplastic resins such as styrene resins such as ABS resin, polyamide resins such as nylon 6 and nylon 6,6, and polyolefin resins such as polyethylene and polypropylene are used in electric / electronic fields, OA / consumer electronics fields,
It is used in the automotive and other fields. Above all, there is an increasing demand for materials having excellent flame retardancy, heat resistance and impact resistance due to an increase in product safety awareness. Conventionally,
In order to improve the flame retardancy of a thermoplastic resin, various flame retardants have been added. However, there is a problem that heat resistance and impact resistance are reduced by using a flame retardant. In addition, there are voices of concern about the use of antimony-based flame retardant aids used in combination with the flame retardant from the viewpoint of safety, and it is desired to reduce the amount of use or no use. On the other hand, in order to improve heat resistance, various inorganic fillers and fillers are blended with a thermoplastic resin, but they are not sufficiently satisfactory in flame retardancy and impact resistance. Further, in order to improve impact resistance, various rubber components and elastomer components have been used or increased in amount. However, there is a problem that heat resistance and flame retardancy are reduced with the use of these components.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has as its object to provide a resin composition having excellent flame retardancy, heat resistance and impact resistance. .

[0002]

According to the present invention, (C) 30 to 99.9% by weight of a thermoplastic resin and (B) 0.1 to 70% by weight of a polycarbodiimide are added to a total of 100 parts by weight of (C) A) a resin composition comprising 0.1 to 50 parts by weight of a functional group-containing aromatic compound and / or an aromatic oligomer; and (D) a flame retardant comprising (A) +
(B) A resin composition comprising 1 to 50 parts by weight per 100 parts by weight. A preferred method for producing the composition is a method in which the component (B) is cured during the melt-kneading of the components (A) to (C) or (A) to (D).

[0003]

BEST MODE FOR CARRYING OUT THE INVENTION In the resin composition of the present invention,
As the component (A), a known thermoplastic resin can be used without any limitation. As the thermoplastic resin (A), for example, ABS resin, AS resin, HIPS, PS,
(Rubber reinforced) styrene resins such as MBS, MS, AES, AAS, etc., polyethylene, polypropylene, polybutene-1, ethylene-vinyl acetate copolymer (EVA),
Polyolefin resin such as ethylene-vinyl alcohol copolymer (EVOH), polyamide resin, thermoplastic polyester resin, polycarbonate resin, wholly aromatic polyester, PPS resin, LCP, vinyl chloride resin (PVC), polysulfone, polyether Ether ketone, (modified) polyphenylene ether resin, polyoxymethylene (POM), polymethyl methacrylate (PM
MA) and the like. These (A) thermoplastic resins can be used alone or in combination of two or more.

The polyamide resin used here is usually a linear resin represented by the general formula H ₂ N— (CH ₂ ) _X —NH ₂ (wherein X is an integer of 4 to 12). a diamine of the general formula HO ₂ C- (CH ₂₎ (in the formula, Y is an integer of 2~12.) _Y -CO ₂ H those produced by polycondensation of linear dicarboxylic acids represented by Etc. can be used.

Preferred examples of these polyamide resins include nylon 6,6, nylon 6,10, nylon 6,12, nylon 6, nylon 12, nylon 11,
Nylon 4, 6 and the like. In addition, nylon 6 /
6,6, nylon 6 / 6,10, nylon 6/12, nylon 6 / 6,12, nylon 6 / 6,6 / 6,10,
Copolyamides such as nylon 6/6, 6/12 can also be used. Also, semi-aromatic polyamides obtained from aromatic dicarboxylic acids such as nylon 6/6, T (T; terephthalic acid component), terephthalic acid, and isophthalic acid, and alicyclic diamines; Polyamides and polyesteramides obtained from a diamine and the above-mentioned linear dicarboxylic acid can also be used. The polyamide resin may be used alone, or two or more kinds may be used in combination.

Examples of the thermoplastic polyester resin include those obtained by polycondensing an aromatic dicarboxylic acid or an ester or an ester-forming derivative thereof with a diol by a known method. Examples of the aromatic dicarboxylic acids include naphthalenedicarboxylic acids such as naphthalene-2,6-dicarboxylic acid, terephthalic acid, isophthalic acid, p-hydroxybenzoic acid, adipic acid, sabacic acid, and the like. Derivatives are also used in thermoplastic polyester resins. Examples of the diol include polymethylene glycol having 2 to 6 carbon atoms such as ethylene glycol, 1,4-butanediol, and 1,6-hexanediol, or
1,4-cyclohexanediol, bisphenol A,
And their ester-forming derivatives. Specific examples of the thermoplastic polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and bisphenol A isophthalate. Among them, PBT and PET are preferable. These thermoplastic polyester resins can be used alone or in combination of two or more.

Preferred thermoplastic resins used for the component (A) are the above-mentioned polyolefin resins, polyamide resins,
Thermoplastic polyester resin, modified polyphenylene ether, polycarbonate, (rubber reinforced) styrene resin, more preferably polyolefin resin, (rubber reinforced) styrene resin, particularly preferably (rubber reinforced) styrene resin . Particularly preferably used as the component (A) of the resin composition of the present invention (rubber reinforcement)
Styrene resin is a monomer component composed of an aromatic vinyl compound or another vinyl monomer copolymerizable with an aromatic vinyl compound and an aromatic vinyl compound in the presence or absence of a rubbery polymer. (Graft) polymer obtained by polymerizing

The rubbery polymer used here includes:
For example, polybutadiene, polyisoprene, butyl rubber,
Styrene-isoprene copolymer (styrene content 5-60
% By weight), a styrene-isoprene copolymer,
Acrylonitrile-butadiene copolymer, ethylene-α
-Olefin copolymer, ethylene-α-olefin-
Polyene copolymer, silicone rubber, acrylic rubber, butadiene- (meth) acrylate copolymer, styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogen Butadiene-based polymer, ethylene-based ionomer and the like. The styrene-butadiene block copolymer and the styrene-isoprene block copolymer include those having an AB type, an ABA type, a tapered type, a radial teleblock type, and the like. Further, the hydrogenated butadiene-based polymer,
In addition to the hydride of the block copolymer, a hydride of a styrene block and a block of a styrene-butadiene random copolymer, and a block having a 1,2-vinyl bond content of 20% by weight or less in polybutadiene; Includes hydrides of polymers composed of polybutadiene blocks having a 2-vinyl bond amount of more than 20% by weight. These rubbery polymers can be used alone or in combination of two or more. As the (rubber reinforced) styrene resin, from the viewpoint of impact resistance, a monomer comprising an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer in the presence of a rubbery polymer is used. A rubber-reinforced styrenic resin obtained by polymerizing the components, or a rubber-reinforced styrenic resin obtained in the presence of a rubbery polymer and obtained by polymerizing the above monomer component in the absence of a rubbery polymer It is preferable to use a mixture with a styrene resin.

(Rubber Reinforcement) Examples of the aromatic vinyl compound used in the styrene resin include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N
-Diethyl-p-aminoethylstyrene, N, N-diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, etc. Styrene and α-methylstyrene are particularly preferred. These aromatic vinyl compounds can be used alone or
A mixture of more than one species is used. The amount of the aromatic vinyl compound used is preferably 20 to 100% by weight, more preferably 30 to 90% by weight, particularly preferably 40 to 80% by weight in the monomer component.

Other vinyl monomers include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methyl acrylate, ethyl acrylate, and the like.
Acrylates such as propyl acrylate, butyl acrylate, amino acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate;
Methacrylic acid esters such as butyl methacrylate, amino methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadodecyl methacrylate, phenyl methacrylate, and benzyl methacrylate;
Unsaturated acid anhydrides such as itaconic anhydride and citraconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N-methylmaleimide, N-butylmaleimide;
Α, such as N- (p-methylphenyl) maleimide, N-phenylmaleimide and N-cyclohexylmaleimide;
an imide compound of β-unsaturated dicarboxylic acid; an epoxy group-containing unsaturated compound such as glycidyl methacrylate or allyl glycidyl ether; an unsaturated carboxylic acid amide such as acrylamide or methacrylamide;
Amino group-containing unsaturated compounds such as aminomethyl methacrylate, aminoether methacrylate, aminopropyl methacrylate and aminostyrene; 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2- Butene, trans-4-hydroxy-2-
Butene, 3-hydroxy-2-methyl-1-propene,
Examples include a hydroxyl group-containing unsaturated compound such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and hydroxystyrene; and an oxazoline group-containing unsaturated compound such as vinyl oxazoline. These other vinyl monomers can be used alone or in combination of two or more. In a (graft) polymer of an aromatic vinyl compound and an imide compound of an α, β-unsaturated dicarboxylic acid, the copolymer of the aromatic vinyl compound and the unsaturated acid anhydride is post-imidized ( (Completely or partially) are also included in the (rubber reinforced) styrenic resin of the present invention. The amount of these other vinyl monomers used is preferably 80% in the monomer components.
0 to 0% by weight, more preferably 70 to 10% by weight, particularly preferably 60 to 20% by weight.

Preferred (rubber-reinforced) styrenic resins include, in the presence of a rubbery polymer, an aromatic vinyl compound and a vinyl cyanide compound, and if necessary, other copolymerizable vinyl monomers. Examples thereof include a combination of a rubber-reinforced styrene resin obtained by polymerization, and an aromatic vinyl compound, a vinyl cyanide compound, and, if necessary, a styrene resin comprising another copolymerizable vinyl monomer. In addition, the functional group-containing (rubber reinforced) styrene resin of the present invention can be obtained by mixing an acrylic acid ester, a methacrylic acid ester, and an unsaturated acid anhydride in the copolymerization component of the above (A) component (rubber reinforced) styrene resin. At least one functional group selected from the group consisting of an unsaturated acid, an epoxy group-containing unsaturated compound, an unsaturated carboxylic acid amide, an amino group-containing unsaturated compound, a hydroxyl group-containing unsaturated compound, and an oxazoline group-containing unsaturated compound Those obtained by copolymerizing a contained vinyl monomer are exemplified. By using this functional group-containing (rubber reinforced) styrene resin in the component (A) in an amount of 0.1 to 80% by weight, preferably 1 to 50% by weight, and particularly preferably 3 to 30% by weight, flame retardancy is obtained. It becomes a resin composition which is more excellent in heat resistance and impact resistance. Here, contains functional group (rubber reinforced)
The amount of the functional group-containing vinyl monomer in the styrene resin is preferably 0.1 to 30% by weight in the monomer component. The preferred amount of the rubbery polymer in the rubber-reinforced styrene resin is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, from the viewpoint of melt viscosity and impact resistance.
Particularly preferably, the content is 20 to 55% by weight. The average particle size of the dispersed particles of the rubber-like polymer in the rubber-reinforced styrene resin is preferably 0.05 to 30 μm from the viewpoint of melt viscosity and impact resistance. The (rubber-reinforced) styrene resin used for the component (A) of the present invention is obtained by emulsion polymerization of a monomer component containing an aromatic vinyl compound as a main component in the presence or absence of a rubber-like polymer. It can be produced by performing radical (graft) polymerization such as suspension polymerization, solution polymerization, or bulk polymerization. Preferably, it is emulsion polymerization. For this emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used. The above monomers or monomer components can be added to the reaction system all at once or continuously.

Examples of the polymerization initiator include organic hydroperoxides represented by cumene hydroxyperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and the like, sugar-containing pyrophosphate formulations, sulfoxylate formulations and the like. A redox system in combination with a reducing agent, or a peroxide such as persulfate, azobisisobutyronitrile, benzoyl peroxide or the like is used. Preferably, it is an oil-soluble initiator, and is a redox system obtained by combining a cumene hydroperoxide, a diisopropylbenzene hydroperoxide, a paramenthane hydroperoxide with a reducing agent represented by a sugar-containing pyrophosphate formulation, a sulfoxylate formulation, and the like. Is good. Moreover, you may combine the said oil-soluble initiator and a water-soluble initiator. When combined, the addition ratio of the water-soluble initiator is preferably 50% by weight or less, more preferably 25% by weight or less of the total amount. Further, the polymerization initiator can be added to the polymerization system all at once or continuously. The amount of the polymerization initiator to be used is generally 0.1 to 1.5% by weight, preferably 0.2 to 0.7% by weight, based on the monomer component. Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, tetraethylthiuram sulfide, and carbon tetrachloride. , Hydrocarbons such as ethylene bromide and pentaphenylethane, or acrolein, methacrolein, allyl alcohol, 2-
Ethylhexyl thioglycolate, a dimer of α-methylstyrene and the like can be mentioned. These chain transfer agents are
They can be used alone or in combination of two or more. The method of using the chain transfer agent is batch addition, split addition,
Alternatively, any method of continuous addition may be used. The amount of the chain transfer agent to be used is usually 0.05 to
It is about 2.0% by weight.

As an emulsifier, an anionic surfactant,
Nonionic surfactants, and amphoteric surfactants are included. Among them, examples of the anionic surfactant include a higher alcohol sulfate, an alkylbenzene sulfonate, a fatty acid sulfonate, a phosphoric acid, and a fatty acid salt. As the nonionic surfactant, an alkyl ester type, an alkyl ether type, an alkyl phenyl ether type or the like of ordinary polyethylene glycol is used. Further, as an amphoteric surfactant,
Those having a carboxylate, a sulfate, a sulfonate, or a phosphate as an anion portion and an amine salt, a quaternary ammonium salt, or the like as a cation portion can be given. The amount of the emulsifier used is usually 0.1 to the monomer component.
It is about 3 to 5.0% by weight. Incidentally, the (rubber reinforced) styrene resin has a polymerization temperature of 10 to 120 ° C., preferably 3 to 120 ° C.
It is desirable to carry out emulsion polymerization under the condition of 0 to 110 ° C.

The graft ratio of the rubber-reinforced styrene resin is preferably 5 to 150% by weight, more preferably 10 to 120% by weight. If the graft ratio is less than 5% by weight, the effect of adding the rubber component is not sufficiently exhibited, and a sufficient impact strength cannot be obtained. On the other hand, if it exceeds 150 parts by weight,
Moldability decreases. Here, graft ratio (% by weight)
Represents the weight of the rubber component in 1 g of the rubber-reinforced styrene resin as X,
When the weight of the methyl ethyl ketone insoluble matter is Y, the value is obtained by the following equation. Graft ratio (% by weight) = [(YX) / X] × 100 The molecular weight of the (rubber reinforced) styrene resin is preferably 0.1 [intrinsic viscosity [η] (soluble matter in methyl ethyl ketone, 30 ° C.). 2-2 dl / g, more preferably 0.3 to
1.8 dl / g. This intrinsic viscosity [η] is 0.2d
If it is less than 1 / g, a high balance of physical properties between rigidity and impact strength cannot be obtained, while if it exceeds 2 dl / g, moldability deteriorates.

When two or more monomer components are used during (graft) polymerization, preferred combinations thereof are as follows. (1) Aromatic vinyl compound / vinyl cyanide compound (2) Aromatic vinyl compound / (meth) acrylate (3) Aromatic vinyl compound / vinyl cyanide compound /
(Meth) acrylic acid ester (4) aromatic vinyl compound / imide compound of α, β-unsaturated dicarboxylic acid (5) aromatic vinyl compound / vinyl cyanide compound /
Imidated α, β-unsaturated dicarboxylic acid (6) Aromatic vinyl compound / (meth) acrylate / Imidized α, β-unsaturated dicarboxylic acid (7) Aromatic vinyl compound / vinyl cyanide compound / Unsaturated acid anhydride (8) aromatic vinyl compound / (meth) acrylate / unsaturated acid anhydride (9) aromatic vinyl compound / vinyl cyanide compound /
(Meth) acrylic acid ester / unsaturated acid anhydride (10) aromatic vinyl compound / imide compound of α, β-unsaturated dicarboxylic acid / unsaturated acid anhydride (11) aromatic vinyl compound / vinyl cyanide compound /
Hydroxyl-containing unsaturated compound (12) aromatic vinyl compound / vinyl cyanide compound /
Epoxy group-containing unsaturated compound (13) Aromatic vinyl compound / vinyl cyanide compound /
Oxazoline group-containing unsaturated compound In the above combination, the unit derived from the aromatic vinyl compound (in the graft chain grafted on the rubbery polymer) is 1
It occupies preferably from 100 to 100% by weight, preferably from 10 to 90% by weight.

The polycarbodiimide used as the component (B) of the present invention will be described below. The polycarbodiimide, for example, the general formula (I) -N = C = N -R 1 - ····· (I) [provided that, R ¹ in the general formula (I) represents a divalent organic group. ] Having a repeating unit represented by the formula (1) can be preferably used. The method for synthesizing the polycarbodiimide is not particularly limited.
By reacting in the presence of a catalyst that promotes the carbodiimidation reaction of the isocyanate group (hereinafter also referred to as “carbodiimidation catalyst”), polycarbodiimide can be synthesized.

The organic polyisocyanate used in the synthesis of the polycarbodiimide is preferably an organic diisocyanate. Such organic diisocyanates include, for example, phenylene-1,3-diisocyanate,
Phenylene-1,4-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, 1-methylphenylene-2,4-diisocyanate, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate,
1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, biphenylene-4,4'-diisocyanate, 3,3'-dimethoxybiphenylene-
4,4′-diisocyanate, 3,3′-dimethylbiphenylene-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, 3,3′-dimethoxydiphenylmethane-4, 4′-diisocyanate, 3,
3′-dimethyldiphenylmethane-4,4′-diisocyanate, naphthalene-1,5-diisocyanate, cyclobutylene-1,3-diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,3-diisocyanate, Cyclohexylene-1,
4-diisocyanate, 1-methylcyclohexylene-
2,4-diisocyanate, 1-methylcyclohexylene-2,6-diisocyanate, 1-isocyanate-
3,3,5-trimethyl-5-isocyanatomethylcyclohexane, cyclohexane-1,3-bis (methylisocyanate), cyclohexane-1,4-bis (methylisocyanate), isophorone diisocyanate, dicyclohexylmethane-2,4'- Diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, ethylene diisocyanate, tetramethylene-
1,4-diisocyanate, hexamethylene-1,6-
Diisocyanate, dodecamethylene-1,12-diisocyanate, lysine diisocyanate methyl ester, etc .; and isocyanate prepolymers at both ends obtained by reacting a stoichiometric excess of these organic diisocyanates with a bifunctional active hydrogen-containing compound. Can be mentioned. These organic diisocyanates can be used alone or in combination of two or more.

Other organic polyisocyanates optionally used together with an organic diisocyanate include, for example, phenyl-1,3,5-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, diphenylmethane-2,5 , 4'-triisocyanate, triphenylmethane-2,4 ', 4 "-triisocyanate, triphenylmethane-4,4', 4"-
Triisocyanate, diphenylmethane-2,4
2 ', 4'-tetraisocyanate, diphenylmethane-2,5,2', 5'-tetraisocyanate, cyclohexane-1,3,5-triisocyanate, cyclohexane-1,3,5-tris (methylisocyanate), 3 1,5-dimethylhexane-1,3,5-tris (methyl isocyanate), 1,3,5-trimethylcyclohexane-1,3,5-tris (methyl isocyanate), dicyclohexylmethane-2,4,2'-tri Isocyanate, dicyclohexylmethane-2,4,
Examples include terminal isocyanate prepolymers obtained by reacting a stoichiometric excess of a trifunctional or higher functional organic polyisocyanate such as 4'-triisocyanate with a bifunctional or higher polyfunctional active hydrogen-containing compound. . The above-mentioned other organic polyisocyanates can be used alone or in combination of two or more. The amount of the organic polyisocyanate to be used is usually 0 to 40 parts by weight, preferably 100 to 40 parts by weight per 100 parts by weight of the organic diisocyanate. Is 0-20
Parts by weight.

In the synthesis of polycarbodiimide, an organic monoisocyanate may be added as necessary to appropriately control the molecular weight of the obtained polycarbodiimide when the organic polyisocyanate contains another organic polyisocyanate. By using an organic diisocyanate in combination with an organic monoisocyanate, a polycarbodiimide having a relatively low molecular weight can be obtained. Examples of such organic monoisocyanates include alkyl monoisocyanates such as methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, n-butyl isocyanate, lauryl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, 4-methylcyclohexyl isocyanate, and 12,5. Cycloalkyl monoisocyanates such as -dimethylcyclohexyl isocyanate, phenyl isocyanate, o-tolyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, 2-methoxyphenyl isocyanate, 4-methoxyphenyl isocyanate, 2-chlorophenyl isocyanate, 4-chlorophenyl Isocyanate, 2
Aryl monoisocyanates such as -trifluoromethylphenyl isocyanate, 4-trifluoromethylphenyl isocyanate, and naphthalene-1-isocyanate. These organic monoisocyanates can be used alone or in combination of two or more, and the amount used depends on the desired molecular weight of the polycarbodiimide and the presence or absence of the other organic polyisocyanate. Is 0 to 40 parts by weight, preferably 0 to 20 parts by weight, per 100 parts by weight of the total organic polyisocyanate component.

Examples of the carbodiimidization catalyst include 1-phenyl-2-phospholene-1-oxide,
-Phenyl-3-methyl-2-phospholene-1-oxide, 1-phenyl-2-phospholene-1-sulfide,
1-phenyl-3-methyl-2-phospholene-1-sulfide, 1-ethyl-2-phospholene-1-oxide,
1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-sulfide, 1
-Ethyl-3-methyl-2-phospholene-1-sulfide, 1-methyl-2-phospholene-1-oxide, 1-
Methyl-3-methyl-2-phospholene-1-oxide,
1-methyl-2-phospholene-1-sulfide, 1-methyl-3-methyl-2-phospholene-1-sulfide and phosphorene compounds such as 3-phospholene isomers thereof, iron pentacarbonyl, diiron nonacarbonyl, Metal carbonyl complexes such as tetracarbonylnickel, hexacarbonyltungsten, and hexacarbonylchromium; acetylacetone complexes of metals such as beryllium, aluminum, zirconium, chromium, and iron; and phosphate esters such as trimethylphosphate and triethylphosphate can be given. The above carbodiimidization catalyst can be used alone or in combination of two or more. The amount of this catalyst used is
Per 100 parts by weight of all organic isocyanate components,
It is 0.001 to 30 parts by weight, preferably 0.01 to 10 parts by weight.

The synthesis reaction of the polycarbodiimide can be carried out without a solvent or in a suitable solvent. The solvent may be any solvent that can dissolve the polycarbodiimide by heating during the synthesis reaction.
Dichloroethane, 1,2-dichloroethane, 1,1,1
-Trichloroethane, 1,1,2-trichloroethane,
1,1,1,2-tetrachloroethane, 1,1,2,2
-Tetrachloroethane, pentachloroethane, hexachloroethane, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-
Halogenated hydrocarbon solvents such as trichlorobenzene and trichloromethylbenzene, dioxane, anisole,
Ether solvents such as tetrahydrofuran, tetrahydropyran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, and triethylene glycol monomethyl ether; Cyclohexane, 2-acetylcyclohexane, 2-methylcyclohexane, 3-methylcyclohexane, 4-methylcyclohexane, cycloheptanone, 1-decalone, 2-decalone, 2,4-dimethyl-3-pentanone, 4,4-dimethyl- 2-pentanone, 2-methyl- - hexanone, 5-methyl-2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3
-Heptanone, 2,6-dimethyl-4-heptanone, 2
-Octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone,
Ketone solvents such as 4-decanone, aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, cumene, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone , N-methyl-3-pyrrolidone, N-acetyl-3-
Pyrrolidone, N-benzyl-3-pyrrolidone, formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N, N-methylacetamide, N, N-dimethyl Amide solvents such as acetamide and N-methylpropionamide; aprotic polar solvents such as dimethyl sulfoxide; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-propoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxy Ethyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl It can be mentioned acetate-based solvents such as chromatography ether acetate. These solvents can be used alone or in combination of two or more. In the synthesis of polycarbodiimide, the solvent is used in a proportion such that the concentration of all organic isocyanate components is usually 0.5 to 60% by weight, preferably 5 to 50% by weight. If the concentration of all the organic isocyanate components is too low, the reaction rate will be slow and the productivity will be reduced. On the other hand, if the concentration is too high, the resulting polycarbodiimide may gel during the synthesis reaction.

The concentration of the polycarbodiimide synthesis reaction is as follows:
The temperature is appropriately selected depending on the type of the organic isocyanate component and the carbodiimidization catalyst, but is usually from 20 to 200 ° C. In the synthesis reaction of the polycarbodiimide, the organic isocyanate component may be added in its entirety before the reaction, or a part or all thereof may be added continuously or stepwise during the reaction. In addition, a compound capable of reacting with an isocyanate group is added at an appropriate reaction stage from the early stage to the late stage of the synthesis reaction of the polycarbodiimide, to seal the terminal isocyanate group of the polycarbodiimide, and to adjust the molecular weight of the obtained polycarbodiimide. It can also be added at a later stage of the polycarbodiimide synthesis reaction to regulate the molecular weight of the resulting polycarbodiimide to a predetermined value. Examples of the compound capable of reacting with such an isocyanate group include alcohols such as methanol, ethanol, isopropanol and cyclohexanol, and amines such as dimethylamine, diethylamine and benzylamine. The polycarbodiimide synthesized as described above is separated from the solution as needed. In this case, as a method for separating polycarbodiimide, for example, a polycarbodiimide solution is added to a non-solvent inert to the polycarbodiimide, and the resulting precipitate or oil is separated and collected by filtration or decantation. , A method of separating and collecting by spray drying, and a method of separating and collecting by utilizing a change in the dissolution temperature depending on the temperature of the solvent used in the synthesis of the obtained polycarbodiimide, that is, a method of dissolving the polycarbodiimide immediately after the synthesis. When carbodiimide is precipitated by lowering the temperature of the system, a method of separating and collecting the suspension from the suspension by filtration, and the like, and a method of appropriately combining and separating these methods can be used.

In the present invention, the polycarbodiimide has a number average molecular weight (Mn) in terms of polystyrene, determined by gel permeation chromatography (GPC), of usually from 400 to 500,000, preferably from 1,000 to 500,000.
200,000, more preferably 2,000 to 100,
000. In the present invention, the polycarbodiimide used as the component (B) may be, if necessary, one or more compounds containing a graft reactive group and a carboxylic anhydride group (hereinafter also referred to as “reactive compound”). Grafted resin (hereinafter also referred to as “modified polycarbodiimide”),
Alternatively, by using the modified polycarbodiimide and / or the unmodified polycarbodiimide in combination with an epoxy compound, the curing properties are improved, the rigidity of the obtained resin composition of the present invention is improved, and the inorganic filler is further improved. Impact resistance during use is further improved. Here, the reactive compound used for the synthesis of the modified polycarbodiimide is
It is a compound having a graft reactive group and a carboxylic anhydride group, and can be an aromatic compound, an aliphatic compound, or an alicyclic compound. Among these, the alicyclic compound may be a carbocyclic compound or a heterocyclic compound. The graft-reactive group in the reactive compound means a group that reacts with polycarbodiimide to give a modified polycarbodiimide in which a residue of the reactive compound having a carboxylic anhydride group is grafted. Such a graft-reactive group may be any functional group having active hydrogen, such as a carboxyl group or a primary or secondary amino group. In this reactive compound, one or more same or different graft-reactive groups can be present, and one or more carboxylic anhydride groups can be present. Such reactive compounds include:
For example, trimellitic anhydride, benzene-1,2,3-
Tricarboxylic anhydride, naphthalene-1,2,4-tricarboxylic anhydride, naphthalene-1,4,5-tricarboxylic anhydride, naphthalene-2,3,6-tricarboxylic anhydride, naphthalene-1,2,2,3 8-tricarboxylic anhydride, 4- (4-carboxybenzoyl) phthalic anhydride, 4- (4-carboxyphenyl) phthalic anhydride,
Aromatic tricarboxylic anhydrides such as 4- (4-carboxyphenoxy) phthalic anhydride, pyromellitic monoanhydride monomethyl ester, 3,3 ′, 4,4′-benzophenonetetracarboxylic monoanhydride monomethyl ester,
Aromatic tetracarboxylic monoanhydride monoalkyl esters such as 3,3 ', 4,4'-biphenyltetracarboxylic monoanhydride monomethyl ester, 3-carboxymethylglutaric anhydride, butane 1,2,4- Aliphatic tricarboxylic anhydrides such as tricarboxylic acid-1,2-anhydride and propene-1,2,3, -tricarboxylic acid-1,2-anhydride; 3-amino-4-cyano-5,6- Diphenylphthalic anhydride, 3-methylamino-4-cyano-5
Aminoaromatic dicarboxylic anhydrides such as -methylphthalic anhydride, 3-methylamino-4-cyano-5,6-diphenylphthalic anhydride, aminosuccinic anhydride,
Amino-1,2-butanedicarboxylic anhydride, 4-aminohexahydrophthalic anhydride, N-methylaminosuccinic anhydride, 4-methylamino-1,2-butanedicarboxylic anhydride, 4-methylamino Aliphatic dicarboxylic anhydrides such as hexahydrophthalic anhydride can be mentioned. Among these reactive compounds, trimellitic anhydride is particularly preferred. The above-mentioned reactive compounds can be used alone or in combination of two or more.

The modified polycarbodiimide is prepared by adding at least one reactive compound to a polycarbodiimide having a repeating unit represented by the above general formula (I) in the presence or absence of a suitable catalyst at an appropriate temperature. (Hereinafter, also referred to as “denaturation reaction”). In this case, the polycarbodiimides can be used alone or as a mixture of two or more. The amount of the reactive compound used in the modification reaction is appropriately adjusted depending on the type of the polycarbodiimide, the type of the compound, and the use of the resin composition, and the amount of the repeating unit of the polycarbodiimide represented by the above general formula (I) is 1 mol. Is used such that the amount of the graft reactive group in the reactive compound is 0.01 to 1 mol, preferably 0.02 to 0.8 mol. In this case, if the proportion of the graft-reactive group is less than 0.01 mol, long-time heating is required to cure the polycarbodiimide, while if it exceeds 1 mol, the inherent properties of the polycarbodiimide may be impaired. . In the above modification reaction, the reaction between the graft reactive group of the reactive compound and the repeating unit represented by the general formula (I) of the polycarbodiimide progresses quantitatively, and a graft reaction commensurate with the amount of the compound used is achieved. Is done.

The modification reaction can be carried out without a solvent, but is preferably carried out in a suitable solvent. Such a solvent is not particularly limited as long as it is inert to the polycarbodiimide and the reactive compound and can dissolve them. As this solvent,
Examples thereof include the above-mentioned ether solvents, amide solvents, ketone solvents, aromatic hydrocarbon solvents, aprotic polar solvents and the like used in the synthesis of polycarbodiimide. These solvents can be used alone or in combination of two or more. When the solvent used during the synthesis of the polycarbodiimide can be used for the modification reaction, the polycarbodiimide solution obtained by the synthesis can be used as it is. The amount of the solvent used in the modification reaction is usually 10 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, per 100 parts by weight of the total amount of the reaction raw materials. The temperature of the modification reaction is appropriately selected depending on the types of the polycarbodiimide and the reactive compound, but is usually 100 ° C or lower, preferably -10 to + 80 ° C.

The number average molecular weight (Mn) in terms of polystyrene of the modified polycarbodiimide obtained as described above, determined by gel permeation chromatography (GPC), is generally 500 to 1,000,000, preferably 1,000. ~ 400,000, more preferably 2,000 ~ 200,000. The modified polycarbodiimide obtained as described above is usually used after being separated from a solution. As a method for separating the modified polycarbodiimide obtained as a solution at the time of the synthesis from the solvent, a method similar to the above-described method for separating polycarbodiimide can be exemplified. In the modified polycarbodiimide of the present invention, the graft reactive group in the reactive compound is a polycarbodiimide repeating unit (-N = C = NR).
^It has a structure in which a residue having a carboxylic anhydride group of the compound is grafted by reacting with ^1- ), and has a structure substantially different from the polycarbodiimide before the modification reaction. Therefore, the modified polycarbodiimide has a different property from the polycarbodiimide before the modification reaction, and is mixed with an epoxy compound described below and heated, whereby the curing catalyst is acted on by the action of the carboxylic acid anhydride group in the modified polycarbodiimide. Even if it is not used, it usually has a property of being easily cured at a temperature of 100 to 350 ° C, preferably 150 to 300 ° C.

The epoxy compound used for the polycarbodiimide of the component (B) of the present invention is a compound having one or more epoxy groups in the molecule, and may have a functional group other than the epoxy group. The molecular weight is not particularly limited, but is, for example, 70 to 20,000. Such epoxy compounds include, for example, glycidol, glycidyl acrylate, glycidyl methacrylate,
3,4-epoxycyclohexyl acrylate, 3,4
-Epoxycyclohexyl methacrylate and various epoxy resins. Further, those in which a part of the epoxy compound is substituted with a halogen atom are also preferably used. Preferred epoxy compounds are epoxy resins, examples of which include glycidyl ether type epoxy resins represented by bisphenol type epoxy resins, novolak type epoxy resins, cresol novolak type epoxy resins, etc., glycidyl ester type epoxy resins, and aromatic resins. Group glycidylamine type epoxy resins,
Examples include alicyclic epoxy resins, heterocyclic epoxy resins, liquid rubber-modified epoxy resins, and the like. The above epoxy compounds can be used singly or as a mixture of two or more. The amount used is usually 5 to 500 parts by weight, preferably 10 to 300 parts by weight, per 100 parts by weight of the modified polycarbodiimide. In this case, if the amount of the epoxy compound used is less than 5 parts by weight, the effect of improving the curing rate tends to decrease,
On the other hand, if it exceeds 500 parts by weight, the heat resistance of the resin composition tends to decrease.

The polycarbodiimide (B) of the present invention is thermosetting, and it is preferable to use a non-thermosetting material and to cure it at the time of melt-kneading with other components. A completely cured product may be used. Further, the polycarbodiimide (B) of the present invention is preferably dispersed as dispersed particles in the component (A). The average particle size of the dispersed particles of the component (B) in the resin composition of the present invention is preferably 500 μm or less, more preferably 10 μm or less.
0 μm or less, particularly preferably 0.01 to 50 μm. The average particle size here is a weight average, and the particle size of the dispersed particles can be measured by a method of observing a section of the composition with an electron microscope. Here, the weight average particle diameter is calculated by the following equation. The weight average particle diameter _{(R) = Σn 1 R 1} 4 / Σn 1 R 1 3 n 1: dispersed particles number R _1: the particle size of n ₁ [particle size, at least 500 or more (n
₁ ≧ 500) Measure. The diameter of the dispersed particles observed by an electron microscope does not always maintain a perfect circle, and the average value of the longest diameter and the shortest diameter of the particles is defined as the particle diameter. This average particle size is determined by the component (A),
(B) Component, (C) Component, (D) Component Used Amount, (A)
It can be easily adjusted by the melt viscosity of component / (B) component / (C) component / (D) component, shearing force at the time of kneading, order of addition of each component, and the like. Weight ratio of component (A) and component (B) in the flame-retardant resin composition of the present invention [(A)
/ (B)] is 30/70 to 99.9 / 0.1, preferably 40/60 to 99.8 / 0.2, more preferably 60/40 to 99.5 / 0.5, and particularly preferably. Is 80 /
20 to 99/1. If the amount of the component (A) is less than 30% by weight (the component (B) exceeds 70% by weight), the impact resistance is undesirably reduced, whereas if it exceeds 99.9% by weight, the component (B) becomes Less than 0.1% by weight], resulting in poor flame retardancy and heat resistance.

The functional group-containing aromatic compound (C) of the present invention includes a carboxyl group, a hydroxyl group, an acid anhydride group, an epoxy group, an amide group, an amino group, an amino group, a formyl group, a carbonyl group, an azo group, an azide group, One or more functional groups such as a nitro group, a nitroso group, a sulfone group, an oxazoline group, and a vinyl group in a molecule, preferably 1 to 10, more preferably 1
It is an aromatic compound having from 1 to 4, particularly preferably from 1 to 2. One or more of these functional groups may be contained. Of the above functional groups, preferably carboxyl group, hydroxyl group, acid anhydride group, epoxy group, amino group, formyl group, oxazoline group, particularly preferably carboxyl group, hydroxyl group, amino group, formyl group, Preferred are a carboxyl group and a hydroxyl group. By having one or more functional groups in the molecule, a resin composition having an excellent balance of flame retardancy, heat resistance and impact resistance can be obtained. In particular, when partially or wholly uncured polycarbodiimide of the present invention (B) is used, the above compound having a functional group is melt-kneaded using the above compound (B).
It is preferable because the dispersed particles of the component are further miniaturized and the combustion resistance of the dispersed particles is further improved.

The functional group-containing aromatic compound of the component (C) is
It has the above functional group and one or more aromatic rings, preferably 1 to
It is a compound having 10 and more preferably 1 to 5 in a molecule. When there are a plurality of aromatic rings in the molecule, a bond by an alkyl group such as methyl or ethyl and an unsaturated compound thereof, an ether bond, an ester bond, an amide bond, an azo bond, a carbonyl bond, an imide bond, a sulfonyl bond, and a sulfonamide bond Aromatic rings connected by non-aromatic components such as, or those in which aromatic rings are directly bonded such as biphenyl, and those in which aromatic rings are adjacent to each other such as naphthalene, anthracene, and phenanthrene may be used. Not receive. Among them, it is preferable to use one in which aromatic rings are connected by a non-aromatic component, because the resin composition of the present invention has relatively excellent impact resistance. Particularly, a bond by an alkyl group and its unsaturated compound, an ether bond, an ester bond, an amide bond, and a carbonyl bond are preferable. Further, it is preferable to use a resin in which aromatic rings are directly bonded or a resin in which aromatic rings are adjacent to each other, because char formation is further promoted when the resin composition of the present invention is burned, and flame retardancy is further improved. Particularly preferably, the aromatic rings are adjacent to each other.

The melting point or softening point of the functional group-containing aromatic compound (C) is preferably 50 to 300 ° C., more preferably 100 to 250 ° C., and particularly preferably 120 to 250 ° C.
２２０220 ° C. Within the above range, heat resistance,
It becomes a resin composition which is more excellent in impact resistance. Also,
The content of the aromatic ring in the functional group-containing aromatic compound of the component (C) is preferably 10% or more, more preferably 30% or more, particularly preferably 40% or more, based on the molecular weight.
Most preferably, it is 50% or more. When the content is within the above range, a more excellent flame-retardant resin composition can be obtained. Here, the content of the aromatic ring refers to the molecular weight of the aromatic ring and the unsubstituted portion,
This is the ratio to make the total molecular weight.

Preferred examples of the functional group-containing aromatic compound include p-hydroxybenzoic acid, phthalic acid, terephthalic acid, 2-carboxybenzamide, 1-hydroxynaphthalene, 2-hydroxynaphthalene, 1,3-
Naphthalene diol, 1,5-naphthalene diol,
2,7-naphthalenediol, 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6
-Naphthalenedicarboxylic acid, 1-naphthaleneethanol, 2-naphthaleneethanol, 1-naphthalenemethanol, 2-hydroxy-6-naphthalenecarboxylic acid, 2
-(2-hydroxyethoxy) naphthalene, 1-naphthaleneacetic acid, 2-naphthaleneacetic acid, 1-naphthoylhydrazine, 2-naphthoylhydrazine, 1-naphthalenecarboxamide, 2-naphthalenecarboxamide, 1-
Naphthalenemethylamine, 1-naphthaldehyde, 2-
Naphthaldehyde, 3-hydroxy-2-naphthalenecarboxylic acid phenyl ether, 2-hydroxybiphenyl, 4-hydroxybiphenyl, 2-carboxybiphenyl, 4-carboxybiphenyl, 2-hydroxymethylbiphenyl, 4-hydroxymethylbiphenyl, 9-
Nitroanthracene, phenazine, 1-pyrenebutyric acid, 1
-Pyrenecarboxaldehyde, bisphenol-A,
And the like.

As the aromatic oligomer of the component (C) of the present invention, an oligomeric compound having an aromatic ring in the molecule can be used. The weight average molecular weight of the aromatic oligomer is 5,000 or less, preferably 200 to 3,000, and more preferably 300 to 1,000. The number of aromatic rings contained in the repeating structural unit is 1 or more, preferably 1 to 5, more preferably 1 to 3. The content of the aromatic ring in the repeating structural unit is based on the molecular weight,
Preferably at least 10%, more preferably at least 30%,
It is particularly preferably at least 40%, most preferably at least 50%. When the content is in the above range, the resin composition of the present invention is more excellent in flame retardancy. Here, the content of the aromatic ring is a ratio of the molecular weight of the aromatic ring and the unsubstituted portion to the total molecular weight of the repeating structural unit. Further, the aromatic oligomer may contain the above functional group at the molecular terminal, side chain, or main chain. By having one or more functional groups, a resin composition having a particularly excellent balance of flame retardancy, heat resistance and impact resistance can be obtained. Preferred specific examples of the aromatic oligomer include poly (phenyl ether) oligomer, polycarbonate oligomer, aromatic polyamide oligomer, poly (amide imide) oligomer, poly (ethylene terephthalate), poly (butylene terephthalate), Arylate, wholly aromatic polyester LC
P, polyester-based oligomer such as semi-aromatic polyester-based LCP, etc., epoxy resin-based oligomer, phenolic resin-based oligomer, poly (phenylene sulfide) -based oligomer, polysulfone-based oligomer, poly (ether sulfone) -based oligomer, poly (ether ether ketone) Oligomer, and the like. The amount of the component (C) used in the resin composition of the present invention is (A) + (B)
The amount is 0.1 to 50 parts by weight, preferably 0.2 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, particularly preferably 1 to 10 parts by weight based on 100 parts by weight of the component. When the amount of the component (C) is less than 0.1 part by weight, the effect of improving flame retardancy by use is not exhibited, and when it exceeds 50 parts by weight, heat resistance and impact resistance are poor.

As the flame retardant (D) of the present invention, all known flame retardants can be used, but a halogen-based flame retardant, a phosphorus-based flame retardant, and a flame retardant containing both phosphorus and halogen in the molecule simultaneously are preferable. Is mentioned. Among them, examples of the halogen-based flame retardant include a halogen-containing compound having an epoxy group at both ends represented by the following chemical formula 1.

[0035]

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(Wherein X is a bromine or chlorine atom;
a to d are natural numbers of 1 to 4, and p is 0 or a natural number. The halogen-containing compound represented by Chemical Formula 1 is obtained as a reaction product of halogen-containing bisphenol A and a halogen-containing bisphenol A type epoxy resin. Here, examples of the halogen-containing bisphenol A include tetrabromobisphenol A, dichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol A, and the like. Examples of the halogen-containing bisphenol A type epoxy resin include diglycidyl ether of tetrabromobisphenol A, diglycidyl ether of tetrachlorobisphenol A, diglycidyl ether of dichlorobisphenol A, and diglycidyl ether of dibromobisphenol A. . Particularly preferred is a reaction product of tetrabromobisphenol A and a diglycidyl ether of tetrabromobisphenol A. Further, examples of the halogen-based flame retardant include a halogen-containing compound represented by the following chemical formula 2.

[0037]

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(In the chemical formula 2, X and ad are the same as those in the chemical formula 1, and q is a natural number of 1 to 5.) The flame retardant of the chemical formula 2 is a halogenated bisphenol A constituting the flame retardant of the chemical formula 1. It can be obtained by reacting a type epoxy resin with a halogenated phenol such as tribromophenol, dibromophenol, trichlorophenol and dichlorocresol by heating in the presence of a chlorinated catalyst. Further, as the halogen-based flame retardant, brominated polystyrene represented by the following formula 3 can be given.

[0039]

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(Wherein X is a bromine or chlorine atom,
e is a natural number of 1 to 5, and n is a natural number. The flame retardant of formula 3 is preferably brominated polystyrene obtained by post-bromination or brominated styrene polymerization of polystyrene, and the bromine content is preferably from 68 to 72%, more preferably from 68 to 72%. ７０70% by weight.
In addition, gel permeation chromatography (GP
The weight average molecular weight in terms of C) is preferably in the range of 1500 to 15000. Further, as the halogen-based flame retardant, brominated phthalimide represented by the following formula 4 can be exemplified.

[0041]

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(Wherein X is a bromine or chlorine atom;
f and g are natural numbers of 1 to 4. ) Other halogen-based flame retardants include aromatic halogen compounds, halogenated polycarbonates, halogenated polycarbonate oligomers, halogenated cyanurate resins,
Halogenated polyphenylene ethers and the like are preferred, and preferred are decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromobisphenol A, polycarbonate oligomer of tetrabromobisphenol A, brominated bisphenol-based phenoxy resin, brominated bisphenol-based polycarbonate, and bromide. Polyphenylene ether, decabromodiphenyl oxalide condensate, halogen-containing phosphoric acid ester and the like.

Examples of the phosphorus-based flame retardants include inorganic phosphates such as ammonium polyphosphate, aromatic phosphates such as triphenyl phosphate, alkyl phosphates such as triethyl phosphate, acidic phosphates, and phosphonitrile chloride derivatives. And the like, polymerizable phosphorus compounds such as vinyl phosphate and allyl phosphonate, and red phosphorus-based flame retardants.
These (D) flame retardants can be used alone or
Alternatively, two or more kinds can be used in combination. Among the (D) flame retardants, halogen-based flame retardants having epoxy groups at both ends represented by the above formula (1) are particularly preferable in terms of dispersion in a resin, and phosphorus-based flame retardants are preferable in view of processability. Is preferred. The amount of the halogen-based flame retardant represented by Chemical Formula 1 is
(D) In the flame retardant, preferably 1 to 100% by weight, more preferably 10 to 100% by weight, particularly preferably 20 to 100% by weight.
80% by weight. The amount of the component (D) used in the resin composition of the present invention is 1 to 50 parts by weight, preferably 3 to 4 parts, per 100 parts by weight of the components (A) and (B).
0 parts by weight, particularly preferably 5 to 30 parts by weight.
If the component (D) is less than 1 part by weight, no effect of improving the flame retardancy is obtained, while if it exceeds 50 parts by weight, heat resistance and impact resistance are poor.

Further, a flame retardant auxiliary can be used in combination with the flame retardant (D). Examples of the flame retardant aid include antimony trioxide, antimony tetroxide, antimony pentoxide, chlorinated polyethylene, polyorganosiloxane-based polymer, tetrafluoroethylene polymer, and the like, and these may be used alone. Alternatively, two or more kinds can be used in combination. Here, as the tetrafluoroethylene polymer, an average particle size of 0.05 to 1,000 μm,
Those having a density of 1.2 to 2.3 g / and a fluorine content of 65 to 76% by weight are preferred. Further, those obtained by emulsion polymerization or suspension polymerization are preferably used. The amount of the flame-retardant aid used is the sum of the components (A) + (B) 100
The amount is preferably from 0.1 to 20 parts by weight, more preferably from 0.5 to 10 parts by weight, based on parts by weight.

The composition of the present invention contains glass fiber,
Glass flakes, glass beads, glass fiber milled fiber, hollow glass, carbon fiber, carbon fiber milled fiber, talc, mica, metal fiber, wollastonite, kaolin, barium sulfate, graphite, molybdenum disulfide, zinc oxide whisker, Fillers such as magnesium oxide, potassium titanate whiskers, rock filler, glass balloons, ceramic balloons, pigments such as calcium carbonate, ceramics, titanium oxide, carbon black, and titanium yellow, and metal particles and metal powders having metallic luster, Species can be used alone or in combination of two or more. Among these fillers, glass fibers and carbon fibers have a shape of 5 to 60 μm.
Those having a fiber diameter of m and a fiber length of 30 μm or more are preferred. In addition, these fibers may be used by adding chopped strands during the production of the resin composition of the present invention, or after appropriately impregnating and coating the roving with the component (B) of the present invention and then cutting appropriately. You may. As these fibers, those using a known surface treatment agent or sizing agent may be used. Further, the resin composition of the present invention, a known coupling agent, an antibacterial agent, a fungicide, an antioxidant,
Weather (light) agent, plasticizer, colorant (pigment, dye, etc.),
Additives such as lubricants, antistatic agents and extender oils can be included.

The resin composition of the present invention can be obtained by kneading the components using various extruders, Banbury mixers, kneaders, Brabenders, rolls, Henschel mixers, feeder ruders and the like. The kneading temperature is preferably 100 to 350 ° C, more preferably 150 ° C.
３００300 ° C. When kneading each component, each component may be kneaded at once, or may be added and kneaded in several times. For kneading, an extruder, kneader,
The mixture may be kneaded with a Banbury mixer, a roll, a Brabender, or the like, and then pelletized by an extruder.
In kneading, the polycarbodiimide as the component (B) can be added and used in a cured, semi-cured or uncured state. At this time, the average particle diameter of the component (B) is
Preferably 500 μm or less, more preferably 100 μm
Hereinafter, it is particularly preferable to use a powder finely divided to 0.01 to 50 μm.

The preferred method of using the component (B) is (A)
By hardening the component (B) during melt-kneading of the components (A) to (C) or (A) to (D), a resin composition having more excellent heat resistance and impact resistance can be obtained. As the component (B) at this time, an uncured or semi-cured component can be used, and a mixture thereof may be used. By using the uncured component (B), it is easy to control the dispersion form of the component (B) in the obtained composition at the time of melt-kneading, and it is easy to introduce a component that can react with the component (B). Preferred. as a result,
The flame-retardant resin composition of the present invention will have suitable mechanical properties. Use of the semi-cured component (B) is preferable because the component (B) in the obtained composition has a relatively uniform particle shape and the dispersibility of the component (B) is further improved. (A)-(C) or (A)-
When the component (B) is cured during the melt-kneading of the component (D), as the component (B), the other component (B) cured together with the uncured and / or semi-cured component is used. Preferably, it can be used in an amount of 99% by weight or less, more preferably 90% by weight or less, particularly preferably 10 to 80% by weight in the component (B).

The definitions of "uncured", "semi-cured", and "cured" are not different from those commonly used by those skilled in the art and those commonly used. That is, uncured refers to a state in which the component does not form a three-dimensional crosslinked structure and is soluble in melting. Further, semi-cured means that a three-dimensional cross-linked structure is formed in part or most, and the extraction amount (elution amount) when a solvent in which the uncured portion is soluble is preferably 0.1% by weight or more. , More preferably 0.5% by weight or more, particularly preferably 1% by weight or more. Further, curing means that the amount extracted with the above-mentioned solvent is preferably less than 0.1% by weight, more preferably less than 0.5% by weight, particularly preferably less than 1% by weight. The resin composition of the present invention obtained in this manner is injection-molded, sheet-extruded, vacuum-formed, hetero-formed,
It can be formed into various molded products by foam molding, injection press, press molding, blow molding, gas injection molding and the like. Various molded products obtained by the above molding method utilize the excellent properties thereof, and are used in the OA / home electric appliance field, the electric / electronic field, the communication equipment field, the sanitary field,
It can be used for various parts, housings, chassis, etc. in the field of automobiles and sundries.

[0049]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the examples, parts and% are by weight unless otherwise specified. Each evaluation in the examples is a value measured as follows. The number average molecular weight (Mn) was determined in terms of polystyrene by gel permeation chromatography (GPC). The combustion state after flame contact with the flame-retardant test specimen was observed and evaluated. ○: disappeared naturally. X: continued burning. According to the impact resistance ASTM D256, it was determined Izod impact ¼ "thick test piece (IZ). Units, kg
f · cm / cm. After the box-shaped molded product obtained by heat-resistant injection molding was left in a 110 ° C. gear oven for 1 hour, the deformation state of the molded product was visually evaluated according to the following evaluation criteria. ；: Little deformation. ×: large deformation.

Preparation of rubbery polymers (a) -1 to (a) -5 used in Examples and Comparative Examples Rubber used for (Rubber-reinforced) styrene resin as component (A) of the present invention The polymer in Table 1 was used as the state polymer. (Rubber Reinforcement) Preparation of Styrenic Resin In the presence of the rubbery polymers (a) -1 to (a) -5,
A resin obtained by graft polymerization of various monomer components and a resin obtained by polymerizing only the monomer components without the presence of a rubbery polymer were obtained. Table 2 shows the compositions of these resins. (A) -1, (A) -3, (A) -6, (A)-
8, (A) -10 is emulsion polymerization, and (A) -2, (A)-
4, (A) -5, (A) -7, and (A) -11 were obtained by solution polymerization. (A) -11 was obtained by polymerizing styrene and maleic anhydride copolymer and then imidizing a part of maleic anhydride with aniline.

[0051]

[Table 1]

[0052]

[Table 2]

Thermoplastic resin (A) -12 As a transparent ABS, # 58 manufactured by Nippon Synthetic Rubber Co., Ltd. was used. Nylon 6 [Amilan CM1017 manufactured by Toray Industries, Inc.] was used as the thermoplastic resin (A) -13 polyamide resin. As thermoplastic resin (A) -14 thermoplastic polyester, polybutylene terephthalate (PBT) [PBT-124, manufactured by Kanebo Corporation]
Was used. Panlite L-1225 manufactured by Teijin Chemicals Ltd. was used as the thermoplastic resin (A) -15 polycarbonate.

Polycarbodiimide (B) -1 to (B)-
Preparation 3 (B) -1; polycarbodiimide was obtained by the following method. 50 g of diphenylmethane-4,4'-diisocyanate (MDI) and 3.1 g of phenylisocyanate
And 1-phenyl- in 200 g of cyclohexanone
0.044 3-methyl-2-phospholene-1-oxide
The reaction was carried out at 80 ° C. for 4 hours in the presence of g to obtain a solution of polycarbodiimide (P-MDI) (Mn = 3,500). Thereafter, it was separated and dried. (B) -2: A modified polycarbodiimide was obtained by the following method. To the above polycarbodiimide solution, 3.8 g of trimellitic anhydride was added as a reactive compound and reacted at 20 ° C. for 3 hours to obtain a solution of a modified polycarbodiimide having Mn of 3,800. Thereafter, it was separated and dried. As a result of infrared spectroscopy, this modified polycarbodiimide showed infrared absorption (wave number 2,150 to
2,100 cm ^-1 ) and infrared absorption (wave number 1,850 to 1,780 cm ^-1 ) characteristic of carboxylic anhydride. (B) -3: A modified polycarbodiimide using an epoxy compound in combination was obtained as follows. An epoxy resin comprising a glycidyl ether derivative of bisphenol A [Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.] as an epoxy compound was added to the above-mentioned modified polycarbodiimide solution at a solid content of 20 g of modified polycarbodiimide in the above solution.
After adding 20 g, the solution was filtered under pressure using a filter having a pore size of 1 μm, and cyclohexanone was further added so that the total solid concentration in the solution was 20%, to adjust the solution. Then, it was degassed under vacuum to obtain a paste-like resin.

Functional group-containing aromatic compound (C) -1
(C) -3 The following were used as the functional group-containing aromatic compound of the component (C). (C) -1; 2,6-naphthalenedicarboxylic acid (C) -2; 1-naphthoic acid (C) -3; 9-anthracenecarboxylic acid (C) -4; bisphenol A aromatic oligomer (C) -5 to (C) -6 The following aromatic oligomers were used as the component (C). (C) -5: bisphenol A-based polycarbonate oligomer, weight average molecular weight 1000 (C) -6: poly (phenylene ether) oligomer,
Adjustment of Weight Average Molecular Weight 850 Flame Retardant (D) (D) -1: Prasam EC-20 (brominated epoxy resin) manufactured by Dainippon Ink Co., Ltd. was used as the flame retardant. (D) -2: Antimony trioxide was used as a flame retardant aid.

Examples 1 to 22 and Comparative Examples 1 to 5 The components shown in Tables 3 to 5 were mixed by a mixer for 3 minutes, melt-kneaded in a kneader set at a temperature of 180 to 240 ° C., and then fed to a feeder ruder. And pelletized. The pellet was dried to a moisture content of 0.1% or less, and a test piece for measuring flame retardancy, heat resistance and impact resistance was prepared by press molding, and evaluated by the above-mentioned evaluation method. Table 3 ~
It is shown in FIG.

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

[Table 5]

As is clear from Examples 1 to 22, the resin composition of the present invention is excellent in flame retardancy, heat resistance and impact resistance. In Comparative Example 1, the components (A) and (B) are out of the range of the present invention, and are inferior in flame retardancy and heat resistance. In Comparative Example 2, the components (A) and (B) are out of the scope of the present invention,
Poor impact resistance. Comparative Example 3 is a case where the component (C) is small outside the range of the present invention, and is inferior in flame retardancy. Comparative Example 4 is a case where the component (C) is large outside the range of the present invention, and is inferior in impact resistance. Comparative Example 5 is a case where the component (D) is large outside the range of the present invention, and is inferior in heat resistance and impact resistance.

[0061]

The resin composition of the present invention is excellent in flame retardancy, heat resistance and impact resistance, and can be used in a wide range of applications, for example, OA / home electric appliance field, electric / electronic field, communication apparatus field. , Sanitary field, automobile field, housing related fields such as furniture and building materials, various parts such as miscellaneous goods field, housing,
It can be used for chassis etc.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Hisao Nagai 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. A functional group (C) with respect to (A) 30 to 99.9% by weight of a thermoplastic resin and (B) 0.1 to 70% by weight of a polycarbodiimide (A) + (B) = 100 parts by weight. A resin composition comprising 0.1 to 50 parts by weight of an aromatic compound and / or an aromatic oligomer. 2. The method according to claim 1, wherein (A) + (B) = 10.
0.1 to 50 parts by weight of (C) a functional group-containing aromatic compound and / or an aromatic oligomer to 0 parts by weight,
(D) A resin composition comprising 1 to 50 parts by weight of a flame retardant.